KR20080007355A - Cleaning liquid for lithography - Google Patents
Cleaning liquid for lithography Download PDFInfo
- Publication number
- KR20080007355A KR20080007355A KR1020077025966A KR20077025966A KR20080007355A KR 20080007355 A KR20080007355 A KR 20080007355A KR 1020077025966 A KR1020077025966 A KR 1020077025966A KR 20077025966 A KR20077025966 A KR 20077025966A KR 20080007355 A KR20080007355 A KR 20080007355A
- Authority
- KR
- South Korea
- Prior art keywords
- cleaning liquid
- lithography
- resist
- photoresist
- cleaning
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 238000001459 lithography Methods 0.000 title claims abstract description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 25
- 150000005224 alkoxybenzenes Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 9
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 17
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000011877 solvent mixture Substances 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- -1 glycol ethers Chemical class 0.000 description 10
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical group COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 9
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YZGQDNOIGFBYKF-UHFFFAOYSA-N Ethoxyacetic acid Chemical compound CCOCC(O)=O YZGQDNOIGFBYKF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- JEPGPKGGSYXGKV-UHFFFAOYSA-N 2-ethoxybutanoic acid Chemical compound CCOC(CC)C(O)=O JEPGPKGGSYXGKV-UHFFFAOYSA-N 0.000 description 1
- GVSTYPOYHNVKHY-UHFFFAOYSA-N 2-methoxybutanoic acid Chemical compound CCC(OC)C(O)=O GVSTYPOYHNVKHY-UHFFFAOYSA-N 0.000 description 1
- ICPWFHKNYYRBSZ-UHFFFAOYSA-N 2-methoxypropanoic acid Chemical compound COC(C)C(O)=O ICPWFHKNYYRBSZ-UHFFFAOYSA-N 0.000 description 1
- IWYCSUJIBODXSK-UHFFFAOYSA-N 2-propoxybutanoic acid Chemical compound CCCOC(CC)C(O)=O IWYCSUJIBODXSK-UHFFFAOYSA-N 0.000 description 1
- CPCVNVLTHQVAPE-UHFFFAOYSA-N 2-propoxypropanoic acid Chemical compound CCCOC(C)C(O)=O CPCVNVLTHQVAPE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NQYKGEPHDRUFJL-UHFFFAOYSA-N ethyl 4-ethoxybutanoate Chemical compound CCOCCCC(=O)OCC NQYKGEPHDRUFJL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- VHDGWXQBVWAMJA-UHFFFAOYSA-N methyl 4-methoxybutanoate Chemical compound COCCCC(=O)OC VHDGWXQBVWAMJA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
Landscapes
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
본 발명은, 리소그래피기술에 의해 레지스트패턴을 제조할 때에 이용하는 세정액으로서, 특히 기판 위에 형성한 레지스트막의 불필요한 부분이나 포토레지스트공급장치에 잔류한 포토레지스트조성물을 용해하여, 제거하는 데에 매우 적합한 리소그래피용 세정액에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a cleaning liquid for use in the manufacture of resist patterns by lithographic techniques, and is particularly suitable for lithography for dissolving and removing unnecessary portions of resist films formed on substrates and photoresist compositions remaining in photoresist supply devices. It relates to a cleaning liquid.
반도체소자나 액정표시소자 등에 이용하는 기재(基材)는, 일반적으로 실리콘웨이퍼나 유리기판 위에 포토레지스트를 도포하고, 포토레지스트패턴을 형성시키는 공정을 경유해서 제조된다. 이 포토레지스트를 기판 표면에 도포할 때에, 기판의 에지부분이나 이면부에 레지스트가 부착되고, 그 후에 실행하는 레지스트패턴형성 시의 장해가 되기 때문에, 이 불필요한 레지스트를 미리 세정해서 제거할 필요가 있다. 또, 포토레지스트공급장치에 대해서는, 장치 내에 잔존하여, 부착되어 있는 불필요한 포토레지스트 잔류물을 제거할 필요가 있다.BACKGROUND ART Substrates used for semiconductor devices, liquid crystal display devices, and the like are generally manufactured through a process of coating a photoresist on a silicon wafer or a glass substrate and forming a photoresist pattern. When the photoresist is applied to the substrate surface, the resist adheres to the edge portion or the back surface portion of the substrate, and it becomes a obstacle in forming a resist pattern to be performed later. Therefore, it is necessary to clean and remove this unnecessary resist in advance. . In addition, for the photoresist supply apparatus, it is necessary to remove unnecessary photoresist residues remaining in the apparatus.
이들의 목적으로 이용하는 세정액으로서는, 불필요한 레지스트를 효율적으로 용해 제거할 수 있고, 또한 신속히 건조시키며, 또한 세정 후의 레지스트막의 특성을 손상시키지 않는 용제가 이용되고 있다.As a cleaning liquid used for these purposes, the solvent which dissolves and removes unnecessary resist efficiently, dries quickly, and which does not impair the characteristic of the resist film after washing | cleaning is used.
또, 표면에 포토레지스트막을 형성한 기판을 이용해서, 레지스트패턴을 제조 할 때에, 사용하는 장치, 배관, 기구 등에 포토레지스트의 잔류물이 석출하여 부착건조됨으로써, 이후의 조작에 지장을 초래하는 경우가 있으며, 이 레지스트 부착물을 용해 제거하기 위한 세정제로서도, 다종다양한 용제가 이용되고 있다. 그리고, 이들의 세정제로서는, 레지스트의 부착건조물을 가능한 한 단시간에 완전히 용해 제거할 수 있으며, 또한 후속 처리공정에 악영향을 미치지 않는 것이 요망되고 있다.In the case of manufacturing a resist pattern using a substrate having a photoresist film formed on its surface, residues of the photoresist precipitate and adhere to the equipment, piping, and mechanism to be used, and thus cause trouble in subsequent operations. In addition, various solvents are used as cleaning agents for dissolving and removing this resist deposit. As these cleaning agents, it is desired that the adhered dry matter of the resist can be completely dissolved and removed in the shortest possible time, and that it does not adversely affect subsequent processing steps.
그런데, 이들 세정제의 상당수는, 특정의 에테르계 용제, 에스터계 용제 또는 이들의 혼합물, 혹은 이들과 특정의 케톤계 용제, 락톤계 용제 또는 알코올계 용제와의 혼합물을 주성분으로 하고 있다.By the way, many of these detergents have a specific ether solvent, an ester solvent, or a mixture thereof, or a mixture of these and a specific ketone solvent, a lactone solvent, or an alcohol solvent as a main component.
그리고, 지금까지, 예를 들면 특정의 에테르계 용제를 주성분으로 하는 것으로서, 에틸렌글리콜, 프로필렌글리콜 또는 다이프로필렌글리콜의 저급알킬에테르와 같은 글리콜에테르류에 염기성 물질을 용해한 레지스트제거용 세정액(JP9-269601A), 다이프로필렌글리콜모노저급알킬에테르로 이루어지는 레지스트제거제(JP9-31147A), 프로필렌글리콜알킬에테르와 케톤과 락탐류 또는 락톤류로 이루어지는 레지스트세정제거용 용제(JP11-218933A), 프로필렌글리콜알킬에테르, 에틸렌글리콜알킬에테르 또는 알콕시뷰탄올과 저급알코올로 이루어지는 리소그래피용 세정제(JP11-44960A) 등이 공지되어 있다. 특정의 에스터계 용제를 성분으로 하는 것으로서, 모노옥소카르복시산에스터와 케톤으로 이루어지는 레지스트세정용 용제(JP4-130715A), 아세트산뷰틸 또는 락트산에틸과 프로필렌글리콜모노알킬에테르로 이루어지는 레지스트세정제거용 용제(JP7-128867A), 에틸락테이트와 에틸-3-에 톡시프로피오네이트로 이루어지는 포토레지스트세정용 시너조성물(JP10-104847A), 아세트산알킬 또는 락트산알킬과 알코올로 이루어지는 리소그래피용 세정제(JP11-44960A), 락트산알킬과 프로필렌글리콜모노알킬에테르아세테이트와 케톤으로 이루어지는 포토레지스트제거용 시너조성물(JP2005-128529A) 등이 공지되어 있다.And, until now, for example, as a main component of a specific ether solvent, a resist removal cleaning liquid in which a basic substance is dissolved in glycol ethers such as ethylene glycol, propylene glycol or lower alkyl ether of dipropylene glycol (JP9-269601A) ), Resist removal agent consisting of dipropylene glycol monolower alkyl ether (JP9-31147A), resist cleaning removal solvent consisting of propylene glycol alkyl ether and ketone and lactams or lactones (JP11-218933A), propylene glycol alkyl ether, ethylene BACKGROUND ART A cleaning agent for lithography (JP11-44960A) consisting of glycol alkyl ether or alkoxybutanol and lower alcohol is known. A resist cleaning solvent consisting of a specific ester solvent, consisting of a monooxocarboxylic acid ester and a ketone (JP4-130715A), a solvent for removing the resist cleaning consisting of butyl acetate or ethyl lactate and propylene glycol monoalkyl ether (JP7- 128867A), thinner composition for cleaning photoresist (JP10-104847A) consisting of ethyl lactate and ethyl-3-ethoxypropionate, cleaning agent for lithography (JP11-44960A) consisting of alkyl acetate or alkyl lactate and alcohol, alkyl lactate And a thinner composition for removing photoresist (JP2005-128529A) comprising propylene glycol monoalkyl ether acetate and ketone is known.
그런데, 이들의 세정액에 대해서는, 반도체제조라인에 설치되는 리소그래피용 세정액의 공급배관의 수가 한정되어 있기 때문에, 공통되는 사용목적, 구체적으로는, 컵 내 세정, 기판 에지부 세정, 기판 이면부 세정, 배관 세정, 리워크(rework) 세정, 프리웨트(pre-wet) 등에 대해서, 망라적으로 이용 가능한 세정액이 요망되고 있다.By the way, for these cleaning liquids, since the number of supply pipes of the cleaning liquid for lithography provided in the semiconductor manufacturing line is limited, the common use purposes, specifically, in-cup cleaning, substrate edge cleaning, substrate back surface cleaning, There is a demand for a cleaning liquid that can be used in a wide variety of applications such as pipe cleaning, rework cleaning, pre-wet, and the like.
그러나, 지금까지 공지되어 있는 리소그래피용 세정액으로는, 아크릴계 폴리머를 성분으로 하는 ArF 엑시머레이저용 레지스트를 용해하는 것이 곤란하기 때문에, 기판 에지부나 이면부의 세정을 양호하게 실행할 수 없으며, 또한 ArF 엑시머레이저용 레지스트의 잔류물이 부착된 레지스트공급장치내부품(코터 컵이나 배관)으로부터, 이들의 레지스트 불필요한 부분이나 잔류물을 세정제거하는 데에 공통적으로 사용해서 만족시킬 수 있는 효과를 나타낼 수 없었다.However, since it is difficult to dissolve the resist for ArF excimer lasers containing the acrylic polymer as a cleaning liquid for lithography, which has been known so far, it is impossible to satisfactorily clean the substrate edge portion or the back side portion, and also for ArF excimer laser. From the parts (cotter cups or pipes) in the resist supply apparatus to which the residues of the resist adhered, there was no effect that could be satisfactorily used in cleaning and removing unnecessary portions or residues of these resists.
본 발명은, 특히 지금까지의 세정액으로는 충분한 세정을 실행할 수 없었던 ArF사양의 레지스트에 대해서, 균일하게 양호한 세정성을 나타내고, 처리 후의 건조성이 양호하며, 또한 세정에 의해 레지스트의 특성이 손상되지 않는 세정액을 제공하는 것을 목적으로서 이루어진 것이다.In particular, the present invention exhibits uniformly good cleaning properties for the ArF-specific resists that have not been sufficiently washed with the cleaning liquids up to now, good dryness after the treatment, and no damage to the resists due to cleaning. It is an object of the present invention to provide a cleaning liquid which does not.
본 발명자들은, 리소그래피기술을 이용한 레지스트패턴의 제조 시에 매우 적합하게 사용할 수 있으며, 또한 종래의 세정액에 의해서는 제거할 수 없었던 ArF 레지스트의 잔류물에 대해서도 우수한 용해성을 나타내는 세정제를 개발하기 위해서 예의 연구를 거듭한 결과, 알콕시카르복시산알킬에스터 단독 또는 이것과 알콕시벤젠의 혼합물이, ArF 레지스트의 잔류물에 대하여, 종래의 세정제에 비해서, 약 3 ~ 10배의 용해력을 나타내는 것을 발견하고, 이 식견에 의거해서 본 발명을 이루기에 이르렀다.MEANS TO SOLVE THE PROBLEM The present inventors earnestly research in order to develop the washing | cleaning agent which can be used suitably at the time of manufacture of the resist pattern using a lithographic technique, and also shows the outstanding solubility to the residue of the ArF resist which cannot be removed by the conventional washing | cleaning liquid. As a result, it was found that the alkoxycarboxylic acid alkyl ester alone or a mixture of this and the alkoxybenzene showed about 3 to 10 times the solubility of the residue of the ArF resist compared to the conventional cleaning agent. Thus, the present invention has been achieved.
즉, 본 발명은, 알콕시카르복시산알킬에스터 단독 또는 이것과 알콕시벤젠과의 혼합용제로 이루어지는 리소그래피용 세정액을 제공하는 것이다.That is, this invention provides the washing | cleaning liquid for lithography which consists of an alkoxy carboxylic acid alkylester individual or the mixed solvent of this and an alkoxybenzene.
본 발명의 세정제는, 알콕시카르복시산알킬에스터 단독이어도 되며, 알콕시카르복시산알킬에스터와 알콕시벤젠과의 혼합물이어도 된다.The alkoxy carboxylic acid alkyl ester may be sufficient as the washing | cleaning agent of this invention, and the mixture of the alkoxy carboxylic acid alkyl ester and alkoxybenzene may be sufficient as it.
이 알콕시카르복시산알킬에스터는, 카르복시산을 형성하는 탄화수소기의 1개의 수소원자가 알콕시기로 치환된 카르복시산의 알킬에스터이며, 이와 같은 것으로서는, 예를 들면 메톡시아세트산, 에톡시아세트산, 메톡시프로피온산, 에톡시프로피온산, 프로폭시프로피온산, 메톡시부티르산, 에톡시부티르산, 프로폭시부티르산 등의 저급알콕시지방산의 메틸, 에틸, 프로필에스터를 들 수 있다. 이 중에서 특히 바람직한 것은, 3-메톡시프로피온산메틸, 4-메톡시부티르산메틸, 3-에톡시프로피온산에틸, 4-에톡시부티르산에틸이다.The alkoxycarboxylic acid alkyl ester is an alkyl ester of carboxylic acid in which one hydrogen atom of a hydrocarbon group forming a carboxylic acid is substituted with an alkoxy group. Examples of such alkoxycarboxylic acid alkyl ester include methoxy acetic acid, ethoxy acetic acid, methoxy propionic acid and ethoxy. And methyl, ethyl and propyl esters of lower alkoxy fatty acids such as propionic acid, propoxypropionic acid, methoxybutyric acid, ethoxybutyric acid and propoxybutyric acid. Among these, especially preferable is methyl 3-methoxy propionate, methyl 4-methoxybutyrate, ethyl 3-ethoxy propionate, and ethyl 4-ethoxy butyrate.
또, 본 발명의 세정액은 그 용해성의 관점에서, 알콕시카르복시산 알킬에스터와 알콕시벤젠을 혼합용제로서 이용하는 것이 바람직하다. 이와 같은 알콕시벤젠으로서는, 메톡시기, 에톡시기, 프로폭시기, 부톡시기, 펜톡시기와 같은 탄소원자 1 ~ 6개를 가지는 알콕시기로 치환된 알콕시벤젠을 들 수 있다. 이들의 알콕시벤젠은 소망에 따라서 또한 탄소원자수 1 ~ 4의 저급알킬기로 치환되어 있어도 된다. 이와 같은 화합물로서는, 예를 들면 아니솔(anisole), 페네톨(phenetole), 뷰틸페닐에테르, 펜틸페닐에테르, 메톡시톨루엔 등을 들 수 있다. 그 중에서도 아니솔이 가장 바람직하다.Moreover, it is preferable that the washing | cleaning liquid of this invention uses alkoxycarboxylic acid alkylester and alkoxybenzene as a mixed solvent from the viewpoint of the solubility. As such alkoxybenzene, the alkoxybenzene substituted by the alkoxy group which has 1-6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, and a pentoxy group, is mentioned. These alkoxybenzenes may be substituted with lower alkyl groups having 1 to 4 carbon atoms as desired. As such a compound, anisole, phennetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, etc. are mentioned, for example. Among them, anisole is most preferred.
본 발명의 세정제에 있어서는, 이 알콕시벤젠은, 전체질량에 의거하여 50질량%이하의 비율로 함유시키는 것이 바람직하며, 특별히는 30질량%이하로 하는 것이 바람직하다. 일반적으로 리소그래피기술에 있어서 이용하기 위한 세정제로서는, 기판 또는 포토레지스트공급장치에 부착된 포토레지스트의 잔류물 등을 10분 이내에 완전히 용해시키는 것이 요구된다.In the washing | cleaning agent of this invention, it is preferable to contain this alkoxybenzene in the ratio of 50 mass% or less based on total mass, and it is especially preferable to be 30 mass% or less. Generally, as a cleaning agent for use in the lithographic technique, it is required to completely dissolve the residues of the photoresist attached to the substrate or the photoresist supply apparatus within 10 minutes.
본 발명의 세정액을 이용해서 기판 위의 포토레지스트 불필요한 부분을 제거하기 위해서는, 기판 위에 소요되는 레지스트를, 예를 들면 스핀코팅에 의해 도포한 후, 기판 단부 가장자리부분 또는 기체(基體) 이면부 혹은 그 쌍방에, 세정액을 접촉시켜서, 레지스트막의 불필요한 부분을 세정 제거하고, 다음에 건조한다.In order to remove unnecessary portions of the photoresist on the substrate using the cleaning liquid of the present invention, after applying a resist applied on the substrate by, for example, spin coating, the substrate edge portion or the substrate back portion or the substrate Both surfaces are brought into contact with the cleaning liquid, and the unnecessary portions of the resist film are washed and removed, followed by drying.
기판 에지부나 이면부의 불필요한 레지스트가 제거되었는지의 여부는, 단차측정장치나 주사형 전자현미경에 의한 관찰에 의해서 확인할 수 있으며, 또 레지스트공급장치 내의 레지스트 잔류물이 제거되었는지의 여부는, 육안에 의해서 확인할 수 있다.Whether or not the unnecessary resist of the substrate edge portion or the back surface portion has been removed can be confirmed by observation with a step measuring device or a scanning electron microscope, and whether the residue of the resist in the resist supply device has been removed by visual observation. Can be.
다음에 실시예에 의해 본 발명을 실시하기 위한 최선의 형태를 설명하지만, 본 발명은 이들에 의해서 하등 한정되는 것은 아니다.Next, although the best form for implementing this invention by an Example is demonstrated, this invention is not limited at all by these.
실시예 1, 비교예 1 ~ 7Example 1, Comparative Examples 1 to 7
아크릴계 폴리머를 함유하는 ArF용 포토레지스트(토쿄오오카코교사 제품, 제품명 「TArF-P6111」)를, 90℃ 워터배스(water bath) 상에서 60분간 감압 건조시키고, 레지스트 건고물(乾固物)을 형성하였다.ArF photoresist containing an acrylic polymer (manufactured by Tokyo Okaka Co., Ltd., product name "TArF-P6111") was dried under reduced pressure for 60 minutes in a 90 degreeC water bath, and a resist dried material was formed. It was.
다음에, 이 박편(薄片)형상 건고물 100mg을 표 1에 나타내는 세정액 100ml에 침지(25℃)하고, 그 건고물이 완전히 용해될 때까지 필요로 하는 시간을 측정하였다. 그 결과를 표 1에 나타낸다.Next, 100 mg of this flaky dry matter was immersed (100 degreeC) in 100 ml of washing | cleaning liquids shown in Table 1, and time required until the dry matter melt | dissolved was measured. The results are shown in Table 1.
MPM: 메톡시프로피온산메틸 MPM: Methyl methoxypropionate
GBL: γ-뷰티로락톤GBL: γ-butyrolactone
PM: 프로필렌글리콜모노메틸에테르아세테이트PM: propylene glycol monomethyl ether acetate
PE: 프로필렌글리콜모노메틸에테르PE: Propylene Glycol Monomethyl Ether
EL: 락트산에틸EL: ethyl lactate
MIBK: 메틸아이소뷰틸케톤MIBK: methyl isobutyl ketone
CH: 시클로헥사논CH: cyclohexanone
MAK: 메틸아밀케톤MAK: methyl amyl ketone
이 결과에서, 메톡시프로피온산메틸은, 다른 용제에 비해서, ArF 포토레지스트에 대한 용해력이 현저히 높은 것을 알 수 있다.As a result, it turns out that methyl methoxy propionate has the remarkably high solubility to ArF photoresist compared with the other solvent.
실시예 2Example 2
아니솔과 메톡시프로피온산메틸을, 표 2에 나타내는 비율(질량비)로 혼합한 혼합용제를 이용하여, 실시예 1과 동일하게 해서 건고물이 완전히 용해될 때까지 필요로 하는 시간을 측정하였다. 그 결과를 표 2에 나타낸다.Using the mixed solvent which mixed anisole and methyl methoxy propionate in the ratio (mass ratio) shown in Table 2, it carried out similarly to Example 1, and measured the time required until the dry matter melt | dissolves completely. The results are shown in Table 2.
이 결과에서, 메톡시프로피온산메틸을 70질량%이상 함유한 용제는 특히 높은 용해력을 나타내는 것을 알 수 있다.From this result, it turns out that the solvent containing 70 mass% or more of methyl methoxy propionate shows especially high dissolving power.
실시예 3Example 3
직경 200㎜의 실리콘웨이퍼 위에, ArF용 포토레지스트(토쿄오오카코교사 제품, 제품명 「TArF-P6111」)를, 스피너(다이닛폰스크린세이조사 제품, 제품명 「DNSD-SPIN」)를 이용하여, 2500rpm의 회전속도로 10초 동안, 스핀코팅함으로써 막두께 1.35㎛의 레지스트막을 형성시킨 후, 60℃에서 80초 동안 가열건조해서, 샘플을 제작하였다.On a silicon wafer with a diameter of 200 mm, a photoresist for ArF (Tokyo Okako Corp., product name "TArF-P6111") was used, and a spinner (Dainippon Screen-Sale product, product name "DNSD-SPIN") was used to produce 2500 rpm. A spin film was formed at a rotational speed for 10 seconds to form a resist film having a film thickness of 1.35 mu m, and then dried by heating at 60 DEG C for 80 seconds to prepare a sample.
다음에, 실시예 1의 세정제 즉 메톡시프로피온산메틸로 이루어지는 세정액을, 25℃에서 웨이퍼 단부 가장자리로부터 5㎜의 위치에 배치한 노즐로부터 10ml/분의 비율로 분사하고, 레지스트막 단부 가장자리부분을 세정한 후, 30초 동안 풍건(風乾)시켰다.Next, the cleaning agent of Example 1, that is, a cleaning liquid composed of methyl methoxypropionate was sprayed at a rate of 10 ml / min from a nozzle placed at a position of 5 mm from the wafer end edge at 25 ° C., and the edge portion of the resist film was washed. After that, air drying was performed for 30 seconds.
이와 같이 처리된 레지스트막 단부 가장자리부분을, 촉침식 표면형상측정기(알백(ULVAC)사 제품, 제품명 「DEKTAK8」)를 이용해서 스캐닝하고, 단면방향의 확대패턴형상을 측정하였다. 이 결과, 단부 가장자리부분 이외의 레지스트막 표면은 거의 영향을 받지 않고, 단부 가장자리부분의 불필요한 부분만이 거의 제거되어 있는 것을 알게 되었다.The end edge portion of the resist film thus treated was scanned using a stylus type surface shape measuring instrument (manufactured by ULVAC, product name "DEKTAK8"), and the enlarged pattern shape in the cross-sectional direction was measured. As a result, it was found that the surface of the resist film other than the end edge portion was hardly affected, and only unnecessary portions of the end edge portion were almost removed.
실시예 4Example 4
실시예 1의 세정제 대신에, 아니솔과 메톡시프로피온산메틸의 혼합비율 30 : 70의 혼합물로 이루어지는 세정제를 이용해서, 실시예 3과 동일한 샘플에 대해서 동일한 처리를 실시하였다. 다음에, 실시예 3과 동일하게 해서 레지스트막 단부 가장자리부분의 형상을 측정했던바, 단부 가장자리부분 이외의 레지스트막 표면은, 거의 영향을 받지 않고, 단부 가장자리부분의 불필요한 부분만이 거의 제거되어 있는 것을 알게 되었다.Instead of the cleaning agent of Example 1, the same treatment was performed on the same sample as in Example 3, using a cleaning agent composed of a mixture of anisole and methyl methoxypropionate in a mixing ratio of 30:70. Next, the shape of the resist film end edge portion was measured in the same manner as in Example 3, and the resist film surfaces other than the end edge portion were hardly affected, and only unnecessary portions of the end edge portion were almost removed. I found out.
비교예 8Comparative Example 8
실시예 1의 세정제 대신에, 메톡시프로피온산메틸과 프로필렌글리콜모노메틸에테르의 혼합비 50 : 50의 혼합용제로 이루어지는 세정액을 이용해서, 실시예 3과 동일한 샘플에 대해서 동일한 처리를 실시하였다. 다음에, 실시예 3과 동일하게 해서 레지스트막 단부 가장자리부분의 형상을 측정했던바, 단부 가장자리부분에 있어서의 불필요한 부분은, 거의 제거되어 있지 않았다.Instead of the cleaning agent of Example 1, the same treatment was performed on the same sample as in Example 3 using a cleaning solution composed of a mixed solvent of methyl methoxypropionate and propylene glycol monomethyl ether in a mixing ratio of 50:50. Next, in the same manner as in Example 3, the shape of the edge portion of the resist film was measured, and almost no unnecessary portion was removed at the edge portion.
본 발명에 의하면, 종래부터 공지되어 있는 용제에 비해서 약 3 ~ 10배의 용해력으로 기판 위의 레지스트 불필요한 부분이나, 포토레지스트공급장치 내의 코터 컵, 배관, 접속 개소 등에 잔류한 레지스트, 특히 아크릴계 폴리머의 잔류물을 효율적으로 용해 제거할 수 있다.Advantageous Effects of Invention The present invention provides resists, particularly acrylic polymers, that remain undesired on the substrate or in the coater cups, piping, connections, etc. in the photoresist supply apparatus with a solvent power of about 3 to 10 times that of conventionally known solvents. The residue can be dissolved and removed efficiently.
따라서, 본 발명의 세정액은, 기판 위에 레지스트를 도포할 때에 발생하는 단면부, 이면부의 불필요한 부분에 있어서의 레지스트를 제거하고, 불필요한 부분의 존재에 기인하는 제품 결함의 발생을 방지할 수 있으므로, 배관 세정, 리워크 세정, 프리웨트 등 다방면으로 이용할 수 있다.Therefore, the cleaning liquid of the present invention can remove the resist in the unnecessary portions of the cross-section and the rear surface portion generated when the resist is applied onto the substrate, and can prevent the occurrence of product defects due to the presence of the unnecessary portions. It can be used in various fields such as washing, rework washing and prewet.
Claims (7)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005219373A JP2007034067A (en) | 2005-07-28 | 2005-07-28 | Cleaning liquid for lithography |
| JPJP-P-2005-00219373 | 2005-07-28 |
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| KR20080007355A true KR20080007355A (en) | 2008-01-18 |
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| JP5658941B2 (en) * | 2010-08-05 | 2015-01-28 | 東京応化工業株式会社 | Resist pattern forming method |
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| JP2951216B2 (en) * | 1994-09-22 | 1999-09-20 | 三菱レイヨン株式会社 | Detergent composition |
| JPH11282162A (en) * | 1998-03-26 | 1999-10-15 | Jsr Corp | Manufacture of hardened film |
| JP2004333991A (en) * | 2003-05-09 | 2004-11-25 | Shin Etsu Chem Co Ltd | Method for removing resist component |
| TWI276929B (en) * | 2003-12-16 | 2007-03-21 | Showa Denko Kk | Photosensitive composition remover |
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| JP2007034067A (en) | 2007-02-08 |
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